Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/87—Preparation of ketenes or dimeric ketenes
  • C07C45/89—Preparation of ketenes or dimeric ketenes from carboxylic acids, their anhydrides, esters or halides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/88—Ketenes; Dimeric ketenes
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/03—Non-macromolecular organic compounds
  • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
  • D21H17/17—Ketenes, e.g. ketene dimers

Definitions

• the invention relates to long-chain ketene dimers deriving from saturated or unsaturated carboxylic acids and in particular to a process for the preparation of same.
• Ketenes can be perceived as inner anhydrides of carboxylic acids. Most ketenes dimerise or are stable only as dimers, such as the ketenes which derive from higher fatty acids.
• these ketene dimers are prepared by reacting corresponding carboxylic acid chlorides with tertiary amines, more particularly triethyl amine.
• the course of reaction as represented for example by the reaction of lauric acid chloride with triethyl amine, may be depicted as follows.
• the intermediarily formed ketene immediately dimerises into a diketene.
• the amine can be recovered from the amine hydrochloride formed as by-product by mixing an aqueous solution of the hydrochloride with sodium hydroxide solution and separating the organic phase which forms.
• DE-OS 2 327 988 discloses a process in which the amine hydrochloride is separated by briefly washing it with a diluted solution of neutral salt, e.g. with a 10% solution of sodium sulphate.
• a diluted solution of neutral salt e.g. with a 10% solution of sodium sulphate.
• sodium sulphate means the introduction into the process of a further chemical substance, which likewise must be worked up again or disposed of.
• DE-OS 2 927 118 recommends carrying out the conversion of the fatty acid chloride with a mixture of trimethyl amine and some other tertiary amine.
• DE-OS 2 927 118 recommends carrying out the conversion of the fatty acid chloride with a mixture of trimethyl amine and some other tertiary amine.
• this process also requires inert solvents to control the viscosity of the intermediate product.
• this process is also attended with the drawbacks already mentioned above because use has to be made of organic solvents.
• DE-OS 3 434 212 does not describe an essentially different process either, since instead of the otherwise used organic solvent it employs melted wax, which, ultimately, is likewise an organic solvent. Admittedly, this wax does not have to be removed, since it can be used together with the diketene in special paper sizing processes. However, it is not possible to prepare diketenes in the pure form according to this process.
• the carboxylic acid chloride is fed into the recipient at a rate of not more than 1 mole/hour per mole of present triethyl amine.
• an after-reaction time may be adhered to, e.g. of 5 to 30 minutes, more particularly 10-20 minutes.
• the conversion is conveniently carried out at a temperature in the range of 50° to 100°C, more particularly in the range of 55°-65°C.
• the treatment of the reaction mixture is best carried out with an aqueous solution containing 0-50 wt.% of triethyl amine hydrochloride and 3-32 wt.%, preferably 4-6 wt.%, of hydrochloric acid.
• the separation of the aqueous phase from the ketene can take place, int. al., through sedimentation or centrifuging.
• the obtained ketene may be dried by means of countercurrent drying, e.g. with dry nitrogen.
• the amine hydrochloride may be treated in a conventional manner with, say, sodium hydroxide solution to recover the amine.
• the process according to the invention is carried out continuously, with the starting components being continuously fed into an agitator vessel or a loop reactor for carrying out the main reaction, and the after-reaction being carried out in a tubular reactor connected thereto at the outlet side.
• a vessel equipped with an effective stirrer and internal and external heat exchangers is provided to carry out the process according to the invention.
• inlets for the separate dosing of the starting substances an outlet for discharging the reaction mixture and devices for measuring the existing temperature, pressure, and viscosity.
• a highly effective stirrer adapted to the mixing problem such as an appropriately constructed anchor agitator, in order to ensure sufficient backmixing in the reaction medium and heat transfer ratios for the discharge of the enthalpy of reaction.
• the reaction mixture composed of triethyl amine, triethyl amine hydrochloride, and ketene dimer is treated with diluted aqueous hydrochloric acid or an aqueous solution of hydrochloric acid and triethyl amine hydrochloride to neutralise the excess amine and extract the crystalline product TEA.HCl from the mixing phase.
• the reaction mixture is poured into the acid solution or the acid salt solution with stirring.
• the amount of hydrochloric acid used is as much as is required to remain always in the acid pH range of the aqueous solution.
• the obtained ketene is free of residues of organic solvent and contains only a minor quantity of product-typical impurities such as fatty acid anhydrides and fatty acids.
• the separation of the ketene dimer and the further working up/purification thereof can be carried out in a simple manner.
• a cylindrical agitator vessel with thermostatable jacket and an effective capacity of 1 l ( ⁇ x h: 10 * 14 cm) was equipped with an anchor agitator reaching to the inner wall.
• the anchor agitator in its typical design covers the entire bottom surface and the whole 14 cm cylinder height of the reaction apparatus.
• a thermometer attached at half the inner radius a continuously functioning feeding device for organic acid chlorides in the agitator vessel, and a reflux condenser with superimposed Bunsen valve.
• a commercially available 2 kW circulation thermostat with a liquid volume of 5 l and an external heat exchanger.
• the transport of the heat carrier medium between the thermostat and the double jacket of the reaction vessel was effected via the thermostat's internal pump.
• TEA triethyl amine
• TEA*HCl triethyl amine hydrochloride
• the treatment of the crude product described hereinbelow may serve either to obtain a sample for analytical characterisation, or as a basis for scaled-up separation and purification operations.
• the organic fat phase was then transferred to a round-bottom flask and dried in a rotation evaporator at 65°C under water jet vacuum for 15-30 minutes. A drying loss of 1,02 g (0,76 wt.%) was obtained as a result of the removal of water. The drying process can be speeded up considerably by passing through dry nitrogen.
• the amine salt crystallised out through the removal of water and still containing AKD can then be removed by means of suitable filtration steps. In this way 0,95 g TEA*HCl (0,71 wt.%) were separated.
• the proportion of AKD contained in the product was determined in a known manner by means of morpholine titration and adjusted to the free fatty acid content. As a further characteristic magnitude the acid number, which was determined in accordance with ASTM D 974-64, was taken into consideration.
• the AKD wax characterised by these methods had an AKD content of 90,5% and an acid number of 7 mg KOH/g.
• Example 2 Preparation of AKD in continuous operation with a two-step agitator vessel cascade
• An agitator vessel (1 l) constructed and dimensioned as in Example 1 was connected in cascade with a similar apparatus with an effective capacity of 250 ml.
• stirrer in the second cascade reactor was used an anchor agitator of the same design and arrangement but adapted to the spatial conditions.
• the two reactors had a double-jacket construction, and were connected in series for heating and cooling.
• installed at half the inner radius of the reactors were an internal thermometer and a continuously functioning feeding device for organic acid chlorides and triethyl amine, respectively, and a reflux condenser with superimposed Bunsen valve.
• the reactant use was made of a commercially available 2 kW circulation thermostat with a liquid volume of 5 l and an external heat exchanger. The transport of the heat carrier medium between the thermostat and the double jacket of the reaction vessel was effected via the thermostat's internal pump.
• the required transport of substance between the two cascade vessels takes place via a controllable gear pump kept at 60°C.
• the discharge from the second vessel is so controlled by the appropriate setting of the bottom discharge valve that the filling level was kept at its designated height.
• 230,1 g (2,27 moles) of TEA were charged into the first cascade vessel and brought to a reaction temperature of 60°C. After the rotational speed of the stirrer had been set at 300 rpm, the dosing was started, as in Example 1, of 614,3 g (2,08 moles) of FAC, the rate of feeding being so regulated that the indicated amount was completely transferred to the first reactor in 60 minutes. Immediately on conclusion of the single feeding of FAC, the dosing of TEA to the first reactor was connected up and so regulated, that within 60 minutes 230,9 g (2,28 moles) of TEA were passed to the reactor.
• the (rising) liquid level was then kept at its nominal level by appropriate setting of the gear pump and dosing to the second reactor.
• its bottom valve remained closed in the starting phase and only after the nominal filling level of 250 ml at 60°C had been reached was it opened so far as to give an equilibrium condition.
• An AKD wax obtained according to this example had an AKD content of 91,5% and an acid number of 10 mg KOH/g.
• Example 3 Preparation of AKD in continuous operation with a cascade composed of a loop reactor and an agitator vessel
• An agitator vessel constructed and dimensioned as in Example 2 (1 l) (cascade vessel no. 1) was connected in series with a laminar driven tubular reactor with an effective capacity of 375 ml ( ⁇ internally 9 mm).
• the tubular reactor had a double-jacket construction and was connected in series with the double jacket of the agitator vessel for thermostating. To maintain the nominal filling level in the agitator vessel the reactors were effectively mutually disconnected by means of a controllable gear pump.
• the outlet of the tubular reactor was provided with a small swan neck to prevent it from emptying.
• 230,1 g (2,27 moles) of TEA were charged into the agitator vessel and brought to a reaction temperature of 60°C.
• the dosing was started of 614,3 g (2,08 moles) of FAC, the rate of feeding being so regulated that the indicated amount was passed to the agitator vessel in 60 minutes.
• the dosing of TEA to the first reactor was connected up and so regulated, that within 60 minutes 230,9 g (2,27 moles) of TEA were passed to the reactor.
• the liquid level in the vessel was then kept at its nominal level by appropriate setting of the gear pump and dosing to the connected tubular reactor.
• An AKD wax obtained according to this example had an AKD content of 92,5% and an acid number of 6 mg KOH/g.
• Example 4 Preparation of AKD in continuous operation using a loop reactor and a tubular reactor connected in series
• reaction loop of 380 ml ( ⁇ internally 11 mm) overall content equipped with a gear pump for circulating the reaction product and two spatially separated static mixers on the pressure side for homogeneous feeding of the reactants (FAC follows TEA).
• the reaction temperature was controlled by means of two PT100 detecting elements, which in each case were arranged upstream and downstream of the static mixers.
• the loop branched out in a laminar driven tubular reactor with an effective capacity of 375 ml ( ⁇ internally 9 mm). Steps to disconnect pressure between the reactors, e.g. by means of regulating valves or forced feeding devices, did not prove necessary in this method of operation.
• the reactants FAC and TEA were made available from storage containers and separately dosed into the loop for the respective static mixer via feed pumps.
• the two reaction devices had a double jacket construction and were connected in series for thermostating by means of a circulation thermostat.
• the outlet of the tubular reactor was provided with a small swan neck to prevent emptying.
• the loop was first filled completely with fresh AKD. This was conveniently done by taking melted AKD wax from a storage container and pumping it around the loop until bubbles were no longer to be determined therein. The AKD storage container was then disconnected and the circulation pumping of the AKD continued until the required reaction temperature of 60°C had reached its state of equilibrium. Finally, the volume flow in the loop was set at 100 kg/hour or - taking into account the density of 860 kg/m3 of the mixture of AKD and TEA-HCl - at 116 l/hour.
• An AKD wax obtained according to this example had an AKD content of 91,5% and an acid number of 8 mg KOH/g.

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• Organic Chemistry (AREA)
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• Lubricants (AREA)

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• 1992
  • 1992-12-21 EP EP92204040A patent/EP0550107B1/en not_active Expired - Lifetime
  • 1992-12-21 AT AT92204040T patent/ATE133648T1/de not_active IP Right Cessation
  • 1992-12-21 ES ES92204040T patent/ES2083076T3/es not_active Expired - Lifetime
  • 1992-12-21 DE DE69208071T patent/DE69208071T2/de not_active Expired - Fee Related
  • 1992-12-22 NO NO924984A patent/NO179170C/no not_active IP Right Cessation
  • 1992-12-29 US US07/998,810 patent/US5344943A/en not_active Expired - Lifetime
  • 1992-12-30 FI FI925950A patent/FI106195B/fi active
  • 1992-12-30 CA CA002086452A patent/CA2086452C/en not_active Expired - Fee Related
• 1993
  • 1993-01-04 JP JP5015832A patent/JP2980475B2/ja not_active Expired - Fee Related

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